Prevention of thinning of carbohydrate printing pastes containing diazonium salts with olefin carboxylic acid amides



Patented Nov. 4, 1947 UNITED STATES PATENT OFFICE PREVENTION OF THINNINGOF CARBOHY- DRATE PRINTING PASTES CONTAINING DIAZONIUM SALTS WITH OLEFINCAR- BOXYLIC ACID AMIDES Roy H. Kienle and Frederic Brook, N. J.,assignors to Company, New York, N. Y

Maine No Drawing. Application H. Adams, Bound American Cyanamid acorporation of June 19, 1945,

Serial N0. 600,417

11 Claims.

This invention relates to new compositions containing certain ice colorforming components specifically, it relates to compositions containingacid amides.

An important method of producing prints of azoic colors on vegetablefibers consists in padding the goods with an salt derived from an icecolor diazo component. The diazonium salt is either prepared in solutionbefore use by diazotizing the corresponding amine base, or it Accordingto the present invention, an ice color forming component included in thegroup consisting of compositions containing water-soluble diazoniumsalts and intermediates therefor consisting of amines diazotizable toproduce compositions containing water-soluble diazonium salts areassociated with a water-soluble olefin carboxylic acid amide,represented by the formula:

wherein R is an alkenyl radical containing not more than four carbonatoms; R and R" are radicals selected from the group consisting ofhydrogen, alkyl, omega-hydroxyalkyl and alkenyl radicals containing notmore than four carbon atoms.

When an aromatic amine is diazotized in acid solution, a diazonium saltis formed which is generally assumed to have the following formula:

where Ar stands for the aromatic radical of the diazo stabilized eycomprise such compounds ing referred to as Th diazonium salts.

Itshould be borne in min that also these stabilized diazonium saltsincluding the abovementioned double salts are true diazonium salts,

diazonium salts described above exert the same thinning action.Presumably in aqueous solution, the stabilized diazonium salts areionized to give the same diazonium cation. The pH of theprinting pasteis not critical so long as it is on the acid side and the presentinvention does not deal with any other types of paste. Alkaline media,as is well the diazonium salts to diazo compounds of different structurewhich are referred to as diazotates or nitrosamines.

known, cause rearrangementof Further evidence appears to indicate thatthe thinning action is a colloidal than a chemical reaction. was made: Adiazonium salt derived from 2-nitrO4=-meth0xy aniline was added to aprinting paste made up with a starch thickener; after 20 hours, the thenwater-thin solutionwas coupled with an alkaline solution of betanaphthol and the azo dye formed was removed by filtration. The quantityof azo dyestuil obtained indicated that the bulk of the diazoniumsaltwas-undecomposed while the filtrate still showed the reaction of'starchand not the reaction of reducing sugars. The degree of thinning actiondiffers widely and depends upon the structure of the diazo componentfrom which the diazonium salt is derived. We have found that thosediazonium salts that are known to be very active couplers in theproduction of azo dyestuffs are also the worst thinners, while thosethat are slow in coupling power generally thin to a much lesser degree.Although there is certainly some parallelism in the coupling power andthinning action, these two properties are not strictly proportionate.The diazonium salts that are derived from nitranilines are thephenomenon rather worst thinners; particularly those derived from 2,4dinitro 6 chloroaniline, from 2 nitro 4- chloroaniline, from2-nitro-4-methoxy aniline, from 2-nitro-4-methylanilin thin thevegetable The following test gums very badly. The diazonium-saltsderived from ortho-nitranilines thin more than those derived from themeta and para compounds. On the other hand, the diazonium salts derivedfrom the 2-methyl-4-chloroaniline and from orthoanisidine have onlylittle thinning action. Obviously, the rate of thinning depends upon'theconcentration of the diazonium ions present in the printing paste.

The thinning action has been observed with all thickeners prepared frommaterials of vegetable origin, such as starches, gums, alkylcelluloses,etc. Wheat starch, corn starch, rice starch, sweet potato starch,tapioca starch, and chlorinated starch may be mentioned as examples ofstarches. Carob bean gum and gum mentioned as examples of gums, andmethyl or ethyl cellulose as examples of alkyl celluloses. Ob-- viously,also mixtures of these materials are quite often used as thickeners andtheir viscosity is equally influenced by diazonium salts; It will benoted that all these thickeners are carbohydrates or carbohydratederivatives.

expression fcarbohydrate,thickeneri; is used in a tragacanth may be 7In, the claims, the

broad sense to cover pure carbohydrates and derivatives.

According to the present invention the thinning action of the diazoniumsalts on the carbohydrate printing pastes is inhibited or greatlyreduced by using water soluble olefin carboxylic acid amides. While notcritical the eflective concentration of the thinning inhibitors of thepresentinvention will vary to'a considerable degree with the particulardiazonium compound present in the paste and with the particular thinninginhibitors. In general, from 20 to 50% of thinning inhibitor based onthetotal-weight of the particular amine from'which the diazoniumcompound is produced give optimum results. With certain exceptionaldiazonium compounds amounts of thinning inhibitor be1ow-.20%- areeffective, and in certain other-casesam unts,above 50% may be used withadvantage! The olefin carboxylic acid amides must contain at, least onedouble bond. They may contain more than .one and the nitrogen of theamide may carry one or two alkenyl groups.

Some typical examples of olefin carboxylic acid amides useful in thepresent invention are: propenoic acidgamide (acrylamide), propenoicacid- N -(omega -hydroxy.=-methyl) amide (methylol acrylamide), 2-methylpropenoic acid amide (methyl acrylamide or methacrylamide) A -butenoicacid; amide (crotonamide), A -butenoic acid- N-allylamide .(N-allylcrotonamide), n -butenoic acid-N,N-diallyl amide (-N,N-diallylcrotonamide) N-butenoic N ethylamide (N-ethyl crotonamide), 3-methy1-A-butenoic acid amide (dimethyl-acrylamide), A -butenoic acid amide(vinyl acetamide), n -pentenoic acid amide (betaethyl acrylamide),M-pentenoic acid amide (allyl acetamide), 2-rnethyl-A -butenoic acidamide (tiglic-acid amide), and the like.

Preparation of; these new thinning inhibitors in most casesisaccomplished by the customary procedure ofreacting' the olefincarboxylic acid halide with ammonia or an amine, though in some specificcasespreparation is best accomplished through dehalogenation of thecorresponding dibromo; or dichloroderivative or by dehydrohalogenationof the corresponding mono-bromo or mono-chloro derivative of thesaturatedamide.

Thepresent invention includesall the diazonium salts derived fromice'color diazo compo-.

monofiuoroanilines, 2,5-difluoroaniline, z-fiuoro- 5-chloroaniline,-2,51 dichloroaniline; m-aminobenzotrifluoride, p-amino-benzotrifiuoride,3- amino-4-chlorobenzotrifluoride, 2 methyl 3 chloroaniline, 2-methyll-chloroaniline, Z-methyl-5-chloroaniline, 3-methy1-4-chloroaniline, 5-methyl-Z-chloroaniline, Z-methyl 4 chloro-5 bromoaniline,v2-methyl-4,5-dichloroaniline, 4-

methyl-2,5- dichloroaniline; nitro ,derivatives of anilineandof-itshomologuesand their halogen derivatives, ,as e. g.,. thenitroranilines, Z-methyl- 4-nitroaniline, 2-methyl-5-nitroaniline,l-met-hyl-2-nitroanil-ine,- Z-nitrol-fiuoroaniline,2-nitrol-chloroaniline, ,3-nitro-4-chloroaniline,- 4-nitro-2-chloroani1ine; ether derivatives of primary aromatic amines andtheir halogen derivatives, as e. g., o-anisidine, 2-methoxy-5-methylaniline, 2,5-dimethoxy-aniline, Z-methoxy-lnaphthylamine,2-amino-diphenylether, 2-amino-4-acetyl-diphenylether,benzyl-2-aminophenylether, 3-fluoro-4-methoxyani1ine, 2-methoxy-5-chloroaniline, 2,5-dimethoxyl-chloroaniline,2-methoxy-4-chloro-5-methylaniline, 2 methoxy-5-bromoaniline,3-bromo-6-ethoxy-aniline, 4-chloro 2 amino diphenylether, l-amino-EZ-chloro diphenylether, 4-amino-e-chloro di phenylether, 4,4'-clichloro 2amino diphenylether, 2,2',5-trichloro 4. amino-diphenylether; etherderivatives of aniline and its homologues containing nitro groups as e.g., 2-methoxy-4-nitroaniline, 2-methoxy-5mitroaniline, 2-nitro-4-methoxyaniline, 2-methoxy-4-nitro 5 methylaniline; monoacyl derivativesof aromatic diamines, as e. g., N-hexahydrobenzoyl-p-phenylene diamine,N-hexahydrobenzoyl-p-toluylenediamine, N-benzoyl-p-phenylene diamine;monoacyl derivatives of diamino-phenol ethers, as e. g.,2-benzoyl-amino-4-aminoanisole, Z-hexahydrobenzoyl-amino-5-aminoanisole,2-amino-5-benzoyl-amino-hydroquinone dimethyl ether and diethylether,2-amino-5-hexahydrobenzoyl-aminohydroquinone dimethylether anddiethylether, 2- amino-5-butyrylamino hydroquinone dimethylether anddiethylether, 2-amino-5-phenoxyacetylamino-hydroquinone diethylether,the monomethyl and the monobenzyl and the monophenylurethane of2,5-dia-mino-hydroquinone dimethylether and diethylether,1-amino-3-benzoy1amino- 4,6-dimethoxy-benzene; analogous monoacylderivatives of 2,5-diamino-4-alkoXy-to1uenes and of 2,5-diamino-4-alkoxychlorobenzenes and of 2,5- diamino-e-alkoxy-benzene sulfodialkylamides;analogous monoacyl derivatives of 1,3-diamino- 4,6-dimethylbenzene; thediethylamide of 2-amino-lMJ-chlorophenoxy) -benzoic acid; monoacylderivatives of diaminop-chloropheny1 ethers as e. g.,2-amino-4-chloro-5-acetylamino-diphenylether,2-benzoylamino-4-chloro-5-aminoanisole; amino derivatives of aromaticsulfcnes as e. g., 3- aminol-methyl-diphenyl sulfone, 2-amino-4-methyl-diphenyl sulfone, 2-amino-4-acetyl-diphenyl sulfone, the ethylester of 3-amino-4-(ptoluene-sulfonyl)-benzoic acid, 4-methoxy-3-amino-phenyl-ethyl sulfone, (4-methoxy-3- amino phenyl) benzyl sulfone,4 ethoxy 3 amino-diphenyl sulfone, 2-amino-4-(trifluoromethyl)-phenyl-ethyl sulfone; amino derivatives of aromatic dialkylsulfonamidesas e. g., B-amino- 4-methyl-benzene dimethyl-sulfonamide anddiethylsulfonamide, Q aminol-methoxy-benzene diethylsulfonamide;xenylamine; alpha and beta naphthylamine; alpha aminoanthraquinone; 2-amino-3-nitro-fluorene and 2-amino-3-nitrofluorenone; amino-diarylaminesand their ether derivatives and their nitro derivatives as e. g., 2-methoxy-5-aminodiphenylamine, 4-methoxy-4'- amino diphenylamine, 4ethoxy 4'-amino-diphenylamine, 3,4-dinitro 4 amino diphenylamine;amino-azo compounds, as e. g., 3,2'-dimethyll-amino-azobenzene,2-methyl-4-amino- 5 methoxy 4- chloroazobenzene, 4 amino-4-nitro-3-methoxy-B-methyl-azobenzene, 4-amino-4'-nitro-2,5-dimethoxy-azobenzene, 4-amino-4-chloro-3-methoxy-6-methyl-azobenzene, the azo dye: diazotizedo-anisidine coupled onto alpha naphthylamine.

There are also diazonium salts derived from aromatic diamines in whichonly one of the amino groups is diazotized and they also fall Within thescope of the present invention. An example of this type of amine is2,6-dichloro-1,4-phenylene diamine. Diazonium salts deriving fromdiamines in which both amino groups are diazotized The method ofaddition of the thinning inhibitor is not critical. In general it may beadded in various stages in the production of the diazonium printingpaste. Thus, the aromatic amines used in forming ice color diazocompounds may be blended with the inhibitor and the blends thendiazotized in the customary manner and incorporated into a printingpaste. Another meth- 1 0d is to blend diazotizable amine salts with thehibitor and the inhibitor, which gives the same result on diazotization.A further variant is to dissolve the inbase separately beforediazotization. A second general procedure is to blend the inhibitor withdiazonium salts which are very stable per se, or which may have beenstabilized by conventional means. The blend forms a solid compositionwhich can be incorporated into a printing paste. A variant of the secondprocedure is to add the inhibitor to a prepared diazo solution beforethe printing paste is made up.

The fact that the introduction of the thinner can be effected in so manyways imparts a desirable flexibility to the present invention, which isa practical working advantage.

The above methods of introducing the thinning inhibitor are preferred.However, the invention is not limited thereto. In a number of cases itis possible to mix the diazonium salt with the printing gum and add theinhibitor afterwards. This procedure, however, is not universallyapplicable with full effectiveness because in the case of very activediazo compounds a certain amount of thinning may take place before theinhibitor is added. This somewhat restricts the scope of thismodification, which should normally be used only with diazo compoundswhich do not thin carbohydrates at an excessive rate. With many printingpastes containing diazonium compounds, however, this procedure isefiective and is included within the broad scope of the presentinvention.

The invention will be illustrated in the specific examples whichdescribe typical embodiments of the present invention. The parts are byweight.

Example 1 329 parts of the dry mixture of the zinc chloride double saltof the diazonium chloride derived from 4-methyl-2-nitroaniline and asuflicient quantity of partially dehydrated aluminum sulfate andanhydrous magnesium sulfate to reduce the strength to 23.1% on an aminebasis are intimately mixed with 21.6 parts of acrylamide and 81.4 partsof partially dehydrated aluminum sulfate. This mixture is then dissolvedin 2500 parts of water, and the resulting solution is in- 288 parts of adry mixture of the Zinc chloride pastes have the outstanding advantageover similar pastes which do not contain acrylamide in that'theirrelative viscosities and hence their utility for textile. printing aremaintained much longer than the relative viscosities of similar pasteswhich donot contain this amide. This advantage of the pastes containingthe acrylamide over those which do not is shown in the following table.In this table the relative viscosities shown are the times in secondsfor copper plated steel shot weighing 0.358 gram apiece to fall through130. mm. of the printing paste in a glass .tube of mm. diameter.

Relative Relative .Relative Base Used for Diazonium g g ViscosityViscosity fig g ggf i gggfgg u ed Salt After ,1 Hr. After .3 Hrs. AfterNa hthoic Acid S Mixing Mixing Mixing P Acrylamidc 4-methyl-2-nitroaniline- 20. 5 26. 5 21.0 Bluish red. one 23. 5 2. 5 Less than 0.5.. 0.Acrylamide 29. 8 27. 0 Yellowish red. None 0 24. 5 2.0 Less than 0 o.Acrylamide." 2-methoxy-5enitro aniline. 48. 0 45. 0 44.0. Reddishscarlet. None 0 42. 5 12. 5 6.0 Do. Aerylamide. 2,5-dich1oro aniline 48.5 38.0 40.0 Yellowish scarlct.

do. 34. 5 1. 5 Less than 0.5.. Do. Ortho dian 26.0 22. 5 16.0 Navy blue...do 25. 5 3. 5 Less than 0.5.. Do.

4-methoxy-2-nitro aniline 28.0 23. 5 16.5. Bordeaux. do 25. 5 0.5 Lessthan 0.5.. Do.

double salt of the diazonium chloride derived from2--methoxy-5-nitroaniline and suificient anhydrous magnesium sulfate andpartially dehydrated aluminum sulfate to reduce the strength to 29.1% onan amine basis, are intimately mixed with'32.8 parts of acrylamide and116.2 parts of anhydrous magnesium sulfate. The resulting dry powder isdissolved in 2500 parts of water, and. the solution so obtained isintimately mixed with 7500 parts of 2.5% aqueous carob bean gum.

394 parts of the dry mixture of: the zinc chloride double salt of thediazonium chloride derived from 2,5-dichloro aniline and suificientpartially dehydrated aluminum sulfate to reduce the strength to 20.55%on an amine basis arethoroughly mixed with 20.9 parts of acrylamide. Theresulting dry powder is then dissolved in 2500 parts of water. and thesolution thus prepared is intimately mixed with 7500 parts of 2.5%aqueous carob bean gum.

320 parts of the dry mixture of the zinc chloridedouble salt of thetetrazonium chloride derived from ortho-dianisidine and sufficientanhydrous'magnesium sulfate to reduce the strength to 19.1% on an aminebasis are intimately mixed with 19.3 parts of acrylamide' and 3!? partsof anhydrous sodium sulfate. The resulting mixture isthen dissolved in2500 parts of water, and the solution so made is thoroughly andintimately mixed with 7500 parts of 2.5% aqueous carob gum.

343 parts of a'mixtureof'the 'zinc chloride double salt of the-diazoniumchloride derived from 4-methoxy-2-nitroaniline' and sufficient anhydrousmagnesium sulfate to reduce the strength to 24.5% on an amine basis aremixed with 34 parts of acrylamide and 77 parts of anhydrous sodiumsulfate. The resulting: dry -mixt-ure is then'dissolved in 2500 parts ofwater, and the solution so obtained is thoroughly mixed with 3500-partsof 2.5% aqueous carobbean: gum.

. The six printing pastes described above are useful for the preparationoffast color prints on cloth impregnated with ice color couplingcomponents, 'suchas the anilide .of 2,3-hydroxynaphthoic acid.'Furthermore, theseprinting Example 2 2000 parts of a mixture of thezinc chloride doublesalt of the diazonium chloride derived from4-methyl-2-nitroaniline and sufficient anhydrous magnesium sulfate andpartially dehydrated aluminum sulfate to reduce the strength to 17.6% onan amine basis are intimately mixed with 102.5v parts of methacrylamide(melting point 111-.112 C.). 363 parts of this mixture, which contains4.7% by weight of methacrylamide, are dissolved in 2500 parts of water,and the resulting solution is then intimately mixed with 7.500 parts of2.5% aqueous carob bean gum.

343 parts of mixture of the zinc chloride double salt of. the diazoniumchloride derived from 4- methoxy-2-nitroaniline and sufficient anhydrousmagnesium sulfate to reduce the strength to 24.5% on an amine basis aremixed with 34 parts of methacrylamide and '17 parts of anhydrous sodiumsulfate. The resulting mixture is then dissolved in 2500 parts of waterand the resulting solution is then intimately mixed with 7500 parts of2.5% aqueous carob bean gum.

381 parts of a mixture of the zinc chloride double salt of the diazoniumchloride derived from 4-chloro-2-nitroaniline and sufficient partiallydehydrated aluminum sulfate to reduce the strength to 22.6% onan aminebasis are intimately mixed with 23.2 parts of methaorylamide, and theresulting mixture is dissolved in 2500 parts of water. The solution thusmade is then intimately mixed with 7500 parts of 2.5% aqueous carobbeangum.

The three printing pastes described above are usefulfor the preparationof bright fast color prints on cloth impregnated with ice colorcomponents, such as, for example, th anilide of 2, 3-hydroxy-naphthoicacid. These pastes, containing methacrylamide, retain their viscosity,and hence their usefulness for printing, a much longer time than similarpastes prepared without the use of methacrylamide. This advantage isclearly shown in the following table. In this table, the relativeviscosity figures are the times for .stainless steel spheres weighing1.023 grams apiece or-lead spheres weighing 0.536 gram apiece to fallthrough 130 mm. of the paste in a tube 20 from 4-methoxy-2-nitroanilineand sufficient anmm. in diameter. hydrous magnesium sulfate to reducethe strength Kind of B d U at Di sl zihlerte for gg g, RelativexIfelatiifre Golgi of grinft use so or azonlum e a We lscosl y on hi i eThmmng Inhlbltor Used Salt Viscosity &8? gi gtg 3 Hrs. After 2,3-Hydroxy glziire- Mixing Mixing Mixing Naphtholc Acid 4-methyl-2-nitroami1ine stainlesssteel 16 0 16.0 14.5 bluish red. o do 13 2.0 Less than0.5 Do. 4-lnethoxy-2-nitroaniline- Lead 18 0 17. 5 16.0 Bordeaux. o d 160 0.5 Less than 0.5-. Do. 4-chloro-2-nitro aniline... d 14 0 14.0 12.5yellowish red. do 12 5 2. 0 Less than 0.5 Do. Example 3 15 to 24.5% onan amine basis are mixed with 34 329 parts of a mixture of the zincchloride parts of crotonamide and 77 parts of anhydrous double salt ofthe diazonium chloride derived from sodium sulfate- The resultingmixture is 4-methyl-2-nitroaniline and sufficient partially solved in2500 parts o t d t solu ion dehydrated aluminum sulfate and anhydroushus obtained is intimately mixed with 7500 parts magnesium sulfate toreduce the strength to of aqueous Carob bean 23.1% on an amine basis aremixed with 81.4 parts 381 P rts of a mixture of the zinc chloride ofpartially dehydrated aluminum sulfate and double salt of the diazoniumchloride derived the resulting mixture is dissolved in 2450 parts from4-oh1ero2-nitroani1ine and sufiioient p of water. To this solution isthen added 60 parts tielly dehydrated a um n m su fate to reduce the ofa 36% aqu o l ti of N-methylo] 1 25 strength to 22.6% on an amine basisare mixed amide and the resulting solution is then intiw h parts fcrotonamide. The r su tin mately mixed with 7500 parts of 2.5% aqueousmixture is dissolved in 2500 parts of water, and carob bean gum. thesolution so obtained is then intimately mixed 381 parts of a mixture ofthe zinc chloride w 7500 parts f aq u a b b n sum. double salt of thediazonium chloride derived v The two printing pastes described a v arfrom 4-chloro-2-nitroaniline and suflicient paruseful for thepreparation of fast color prints on tially dehydrated aluminum sulfateto reduce material impregnated with the usual ice color th strength to22.6% on an amine basis are dismp n nts s as t a i f ,3- yd y solved in2440 parts of water to which are then napht c acid. Th se print as s taadded 60 parts of a 36% aqueous solution of their body or viscosity muchbetter than similar N-methylol acrylamide, The resulting solution pa t sade in the Same manner but Without is then intimately mixed with 7500parts of 2.5% crotonamide This is shown n he fo w n aqueous carob beangum. table. In this table the relative viscosities are These printingpastes described above are used the times in seconds for lead spheresweighing for the production of fast color prints on fabrics 40 0.536gram apiece to fall through 130 mm. of the impregnated with ice colorcoupling components paste in a tube 20 mm. in diameter.

B U at D l telatilze {Eftelative Sharia olfclirirt ase se or iazoniumlscosi y lscosi y on n11 e0 Thm'nmg Inhlbltor salt 2:4 3 1 Hr xfter 3Hrs. after 2,3-Hydroxy Mixing Mixing Mixing naphtholc acid Orotonamide4-methoxy-2-nitroaniline 19.5 9.5 5.0 Bordeaux. None d0 16. 0 0.5 Lessthan 0.5.... Do. Orotonamide 4-chloro-2-nitro 13.5 8.0 3.0 yellowishred. None do 12. 5 2. 0 Less than 0.5.-.. Do. such as, for example, theanilide of 2,3-hydroxy- The crotonamide used in this example meltednaphthoic acid. These printing pastes maintain at 159-160 C. and wasprepared from crotonyl their viscosity, and hence are useful for thechloride and liquid ammonia according to the preparation of prints, fora much longer time method of Stoermer et al., Ber, 47, 1789 (1914). thanpastes similarly made but without the N -methylol acrylamide. This isshown in thefol- Example 5 lowing table. 343 parts of a mixture of thezinc chloride dou- In this table, the figures for the relative visblesalt of the diazonium chloride derived from coslties are the times inseconds for copper plated 4-methoxy-2-m'troaniline and sufficientanhysteel shot weighing 0.358 gram apiece to fall drous magnesiumsulfate to reduce the strength to through 130 mm. of the paste in a tube20 mm. 4.5% on an aminebasis are mixed with 77 parts in diameter. ofanhydrous sodium sulfate and the resulting Relative Relative RelativeColor of Print Viscosity Viscosity Thinning Inhibitor Base U 131m" 2Ming, 1 hr. f mum Salt After After 3 Hrs. Aftcr N2, 3 Hfivdrozyd MlxmgMixmg Mixing apht 01c 01 N-meth lola r lamide 4-meth l-2-nitroani1ine28.5 25.0 22.5 bluish red. Nonei luff 110. 23. 5 2. 5 Less than 0.5..--Do N-methylolacrylamide. 4-chloro-2-ni oamlin 30.5 25.0 21.5 yellowishred. None do 24. 5 2.0 Less than 0.5 Do.

Example 4 dry powder is dissolved in 2500 parts of water.

34 parts of a mixture f t Zinc chloride There is then dissolved in thissolution 34 parts double salt of the diazonium chloride derived ofN-allyl crotonamide and the resulting solution same manner except thatthe N-allyl crotonamide is omitted.

The printing pastes prepared. as: described above are'used for thepreparation: oirfastcolor prints on materialimpregnated with ice colorcoupling components such as theanilide of 2,3-hydroxy-, naphthoic acid-The;ormer printing paste, containing the N-allyl crotonamide, maintainsits vis cosity,'and hence its utilityfor printing, much longer thanthe-latter paste'which does not contain this amide. Thisidifference isshown in the following table, in which the relative viscosity figuresare the times. in seconds for lead shot weighing onv an average of0.5365 gram apiece to fall through 130 mmyof the paste in a tube 20 mm.in diameter.

The N-allyl crotonamide is prepared by allowing one molecular proportionof crotonyl chloride to react in ether solution with approximately 3molecular proportions of allyl-amine. The allylamine hydrochloride.formed during. the reaction is filtered off, and the excess allylamineand other are evaporated from the filtrate, leaving the desired N-allylcrotonamide'as a viscous oil.

Paste Con- Paste Containing tairing' No N--Allylv Thinning CrotonamideInhibitor Relative viscosity:

3 mins. after mixing; 11. 10.0 mins. after mixing... 17. 5 5. 5 a hr.after mixing 17. 5 2. 0 1 hr. after mixing. 15. 5 0.5 2 hrs. after.mixing.-. 12.0 Less than 0.5

Example 6 381 parts of a mixture of thezinc chloride'double salt of thediazonium chloride. derived from 4-- chloro-2-nitroaniline andsufficient partially dehydrated aluminum sulfate to reduce the strengthto 2 .6%on an amine basis are dissolved in 2500 parts of water and tothe solution are then added containing. the Neethyl' croton'amide'maintains its. longer, and hence: can :be used by the.

viscosity. printer for a longertimeth'an the latter: which does notcontain this N-ethyl crotonamide. This N-ethylcrotonamide. The resultingdifference is shown by the figures in the foll'owing table, in whichtherelative viscosityfigures are the times in seconds for. sphericallead'shot weighing on an average .0.5365-.gram apiece to fall through130 mm. of .the paste in. a tube. 20mm.

in diameter.

The N-ethyl crotonamide is prepared from crotonyl chloride and anhydrousethylamine in ether solution by the same procedure as thatdescribed inExample 5 for the'prcparation' of N-allylcrotonamide. pared is a paleyellowish oil.

The ,N-ethyl crotonamide thus .pre-.

Paste Gon- Paste Containing taining No N-cthyl Thinning CrotonamideInhibitor Relative Viscosity:

3 mins. after mixing V 13.0 12.5 15 mins. after mixing 12.5 6. 5 30mins. after mixing 10. 5 4. 5 45 mins. after mixing 10. 0 3. 5 1 hr.after mixing 8.0 2.0 1.5 hrs. after mixing 6. 0 0. '1 P Example 7 200parts of 4-methoxy-2-nitroaniline, 50 parts of acrylamide and 150 partsof sodium chloride are thoroughly ground together in a mortar to form ahomogeneous orange powder. This mixture can be used for the preparationof a printing paste which retains its viscosity, and hence its utilityfor printing; a much longer time than a printing paste made from thesame base but without the acrylamide. This is shown by the followingillustration:

168 parts of the mixture of 4-methoXy-2-nitroaniline, acrylamide andsalt described above is thoroughly mixed with 1000 parts of water and325'parts of 5N hydrochloric acid and sufficient ice to lower thetemperature to approximately 5 C. To the resulting slurry is then addedover a period of two or three minutes 550 parts of 1N sodium nitritesolution and the resulting mixture is stirred until diazotizationiscomplete, 15

or 20 minutes being sufficient. The resulting diaz'o solution is thenfiltered to remove small amounts of impurity and diluted with wateruntil it occupies the same volume as 2500 parts of wa ter. This solutionis then intimately mixed With 7500 parts of 2.5% aqueous carob bean gum.

Another printing paste is then made in exact-- ly the same manner exceptthat 84 parts of 4- methoxy-2-nitroaniline are substituted for 168 partsof the mixture of base, acrylamide and salt. The superiority of thepaste made from the base containing the acrylamide is shown in thefollowing table, in which the relative viscosity figures are the timesin seconds for spherical lead shot weighing on an average 0.5365 gramapiece to fall mm. through the paste in a tube 20 mm. in diameter.

Thinning Inhibitor in Printing Paste Acrylamide None Relative viscosity:

2 mins. after mixing 15.0 14. 0 0.5 hr. alter mixing 13. 5 6.5 1 hr.aitermixing 11.5 4.0 1.5 hr.after mixing 10.0 3.0 3 hrs. after mixing 9.0 1.5

Example 8 A thorough mixture is made in a mortar of the followingingredients:

Parts 2-methoxy-4-nitroaniline 200 Methacrylamide (M. P. ill-112 C.) 50

Epsom sa then mixed with 7500 bean gum.

In an entirely similar manner another printing paste is prepared from 84parts of Z-methoxy- 4-nitroaniline alone. These two printing pastes areused for the production of fast prints on the fiber impregnated with icecolor coupling components, for example, for the production of fastbluish red prints on cloth padded with an alkaline solution of theanilide of 2,3-hydroxy-naphthoic acid. The former paste, however, whichcontains the methacrylamide, maintains its viscosity much longer thanthe other and hence is useful for printing for a longer period of time.This is illustrated by the following figures, in which the relativeviscosities are the times in seconds for lead shot weighing on anaverage 0.5365 gram apiece to fall 130 mm. through the paste in a tube20 mm. in diameter.

Thinning Inhibitor Used in Printing Paste Relative Viscosity:

2 mins. after mixing 0.5 hr. after mixing. 1 hr. after mixing 1.5 hrs.after mixing. 2 hrs. after mixing..." 3 hrs. after mixing parts of 2.5%aqueous carob Methacrylamide N one We claim:

1. A composition suitable for the preparation of printing pastescontaining carbohydrate thickeners comprising an ice color-formingcomponent included in the group consisting of compositions containingwater-soluble diazonium salts and intermediates therefor consisting ofamines diazotizable to produce compositions containing Water-solublediazonium salts; the color-forming component having associated therewithan olefin carboxylic acid amide represented by the following formula:

wherein R is an alkenyl radical containing not more than four carbonatoms, R and R". are radicals selected from the group consisting ofhydrogen, alkyl, omega-hydroxyalkyl and alkenyl radicals containing notmore than four carbon atoms; the amount of organic olefin carboxylicacid amide being sufiicient to substantially inhibit thinning of acarbohydrate thickener.

2. A composition suitable for the preparation of printing pastescontaining carbohydrate thickeners comprising an ice color-formingcomponent included in the group of water-soluble diazonium salts; thecolor-forming component having associated therewith an olefin carboxylicacid amide represented by the following formula:

wherein R is an alkenyl radical containing not more than four carbonatoms, R and R" are radicals selected from the group consisting ofhydrogen, alkyl, omega-hydroxyalkyl and alkenyl radicals containing notmore than four carbon atoms, the amount of olefin carboxylic acid amidebeing sufficient to substantially inhibit thinning of the carbohydratethickener.

4. A composition according to claim 1 in which the olefin carboxylicacid amide is propenoic acid amide.

5. A composition according to claim 2 in which the olefin carboxylicacid amide is propenoic acid amide.

6. A composition according to claim 3 in which the olefin carboxylicacid amide is propenoic acid amide.

7. A composition according to claim 1.in which the olefin carboxylicacid amide is 2-methyl propenoic acid amide.

8. A composition according to claim 2 in which the olefin carboxylicacid amide is Z-methyl propenoic acid amide.

9. A composition according to claim 3 in which the olefin carboxylicacid amide is Z-methyl propenoic acid amide.

10. A composition according to claim 2 in which the diazonium salt is adiazonium chloride-zinc chloride double salt.

11. A composition according to claim 3 in which the diazonium salt is adiazonium chloride-zinc chloride double salt.

ROY H. KIENLE. FREDERIC H. ADAMS.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,378,305 Lecher June 12, 19452,378,276 Adams June 12, 1945 2,319,265 Rossander May 18, 1943 2,386,646Adams Oct. 9, 1945

